Metallizable monoazo dipyrazolones



Patented June 7, 1949 STATES 'EZNT F F ICE METALLIZABLE, MONOAZQDIPYRAZOLONES.

Peter Hindermann, Basel, Switzerland; assignor to J; R; Geigy A. G.,Basel, Switzerland NoDrawing. Application December. 3-1, 1946, Se:-rial-No. 719,635. In Switzerland December 27,

Section 1',Public Law 69!), August8; 1946 Patent expires December 2- 7,1965:

aldipyrazolone-of the general formula YC=N\ N=C-Y -z-NH-z :-NH- -'z.-N lone-00" 00 H2 wherein X'st'ands for an oxygen onsulfuratom,

Y stands for a methyl, ethylor phen'yl'group and Z stands for a memberselected from the group:

consisting of radicalsof the benzene seriesbound-in lz l-position and ofradicals of the diphenyl' series boundv in. 4:.Z4'-pOSiti0n.-

Theinew dyestufis form red-brown to dark powtiers.- When subjected'toa-treatment-withmetalyielding'agents either insubstance-or onthe-fibreaccording to usual methods, the new dyestuffs can betransformed" into: metal complex com pounds; The copper.complexcompounds' are iparticularly valuable because ofytheirrexcellentlight fastness... The copperingpcan be effected; as is:

known, for instance witiicopper sulfate in aw neutral. orslightly-acetimacidbathor also in the presence of alkali tartr'ates' inatslightly, alkaline" bath. IIL'thiS wayiorange-rred-or. red"dyeingsaw-ill' be produced, whichlare fast to light andalkalis.

and which often surprisingly possess also: good fastness propertiesriirthe 5111018131 state.- 7

The monoazodyestuffs selected from-the SBIiGSi of 1- (4'-aminophenyl)=3amethyl -pyrazoloneurea are particularly preferred in view of theireasy availability and of theirimproved afiinity for cellulosic fibres.The monoazo dyestuffs from 1- phenyl-( i' -phenyl-4' -amino).-3-methyl-5- pyrazolone-urea compounds are distinguished by aparticularly good water-iastness of the dyeings produced Ont-cellulosicvfibressand zsuhj ected to: ans after-treatment witl-rcoppBrtsalts:

When'l comparedi with: the: known disazo dy' h stuifsproduced from thesame dipyrazolonederivatives, it is a surprising fact thatthe newdyestufis show a good afiinity for cellulosic fibres, whereas'itis knownto anybody skilled'in the art 2 oian azogroupcauses aconversion of a.disazo dyestuii. into a. monoazo dyestuff having a sub-.- stantially.inferior affinity, for. cellulosic fibres.

The same valuable, metallisable. monoazody'estufisare .also obtained byvcondensation of.mon-.-

azo dyestuiis. from l-diazo-6-nitro-2Lhydroxye naphthalenel-sulfonicacid and. from I-( lflaminophenyl)-5-pyrazolone. derivative or 1-.-phenyl- (4-pheny1-4' "-amino) -5.-pyrabo1one derivative with a furthermole of. such a 144'- aminophenyl)-5-pyrazolone derivative or 1'-pheny-l (if -phenyl.-.4-.f -amino) -5.-pyrazolone derivative;respectively in. aknown manner. with phosgene,v thiophosgeneor carbondisulfide, until no more primary amino; groups are present.

The following ,exampleswill illustrate the pres entzinventionwithoutlimiting it. The parts are by weight-unless otherwisestated, while theterm peratures are designated in degrees Centigrade.

EXAMPLE 1 29.5 parts of 1-diazo-6-nitro-2-hydroxynaphthalene-4-sulfonicacid. are combined to the monoazo dyestuff by adding 40.4 parts of ureaof 1- (if -aminophenyl) -3-methyl-5-pyrazolone in the presence of anexcess of.sodium carbonate. Upon stirring the mixture for some hourswhile cooling with ice, the diazo compound disaDDDears:

The dyestuff is isolated by additionof sodium.

chloride and dried; The resulting dyestuff is a dark powder soluble inwater with a red colora-a tion and in concentrated sulfuric acid with amorange coloration. It dyes cellulosic fibres in brown-orangeshades;which, on after-treatmenti Withcopper salts. are changed to red andpossess; substantially improved fastness-properties to light and in themoist'state.

Thesame-dyestufflcan"also be obtained by cou pling 29.5 parts of1-diazo-'-6-nitro-2 hydr0Xy naphthalene-4-sulfonic acid with-18.9 partsof -1- sodaalk alinesolution and condensing the result ant'ami'nomonoazo dyestufi'i with 18.9" parts of 1:" (4 aminophenyl)-3-methyh5-pyrazolone" in a soda alkalinesolutionwithphogene;until nomore= free-amino groups are present. Theso-obtain'ed' dyestuif possessthe'samep'ropert'iesas the above described one.

The urea of 1-(4'-aminophenyl) 3-methyl-5- pyraz'olone mentioned in the!aboveexample can beizpreparediinza known manner by condensing? 3'?I81partsof; 1- 4-samir'1'ophenyl) -3'-methyl-5i-py.-" razolonee in 1 asodar-alkaline solution with phos= gene; until anyfr'ee amino groups:have disap'-- that'igenerally the loss .01; th conjugated.isystenrpeared; The urea is acolorless powder.

EXAMPLE 2 29.5 parts of l-diazo-6-nitro-2-hydroxynaphthalenei-sulfonicacid are combined in the 4 disappears. The dyestufi is isolated byaddition of sodium chloride. The dried dyestuff is a dark powder whichdissolves in water with a red coloration and in concentrated sulfuricacid with an presence of an excess of sodium carbonate with 5 orangecoloration. It dyes cellulosic fibres in 42 parts of thiourea of1-(4-amin pheny brown-orange shades which, when after-treated y-pyrazolone, thus giving the monoazo with copper salts according tousual methods, are dyestuff. Upon stirring this mixture whilecoolconverted into orangeish-red shades of considering with ice, thediazo compound disappears. ably improved fastness properties to lightand in The dyestufi is isolated by addition of sodium the moist state.chloride, filtered and dried. The new dyestufi The urea ofl-phenyl-(4'-phenyl-4-amino)- constitutes a dark powder which i solublein 3-methyl-5-pyrazolone can be obtained by inwater with anorangeish-red coloration and in troducing phosgene into a solution of 53parts concentrated sulfuric acid with an orange coloraof the above saidaminopyrazolone in 500 parts tion and dyes cellulosic fibres inbrown-orange of water in the presence of an excess of sodium shades. Byan after-treatment with copper sulcarbonate and at room temperature,until no fate the color changes to red, while the fastness more freeamino groups can be detected. properties in the moist state and to lightare The corresponding thiourea can be produced substantially improved.under the same conditions by introducing thio- The thiourea of1-(4'-aminophenyl)-3-methyl- 2O phosgene until disappearance of theprimary 5-pyrazolone is obtainable by treating 37.8 parts amino groups.The soda-alkaline solution of of 1-(4-aminophenyl)-3-methyl-5-pyrazolonein the l-phenyl -(4'-phenyl-4"-amino) B-methyla soda-alkaline solutionwith thiophosgene, until 5-pyrazolone can also be condensed according tono more free amino groups can be traced, or by the known method withcarbon disulfide and hycondensing 1-(4-aminophenyl) 3 -methyl-5 drogenperoxide in order to produce the thicpyrazolone with carbon disulfide inthe presence urea. of small quantities of hydrogen peroxide, until Themonoazo dyestufi prepared under the no more free amino groups can bedetected. above mentioned conditions from 29.5 parts of The preparationof 1-(4-aminophenyl)-5- 1-diazo-6-nitro-2-hydroxynaphthalene 4sulpyrazolone may be illustrated by means of the fonic acid and 57.2parts of the thiourea of following example: By condensing 19.2 parts ofphenyl-(4-phenyl-4-amino)-3-methy1-5 py benzoyl-acetic-acid-ethyl esterin boiling alcohol razolone has very similar properties as the abovewith 15.3 parts of p-nitrophenyl hydrazine, the described dyestufi.1-(4-nitrophenyl)-3-phenyl-5-pyrazo1one is ob- The following table setsforth additional extained in good yield. Yellow needles of themeltamples of dyestufis obtainable according to the ing point of 201202C. are thus obtained. By present invention, the process of theirpreparareduction with iron the corresponding 1-(4- tion beingessentially analogous to the process aminophenyl) -3-phenyl 5 pyrazoloneis prodescribed in the preceding examples.

Table Shade of the coppered N0, Diazo-compound Dipyrazolone according toformula I dyemg onto celluloslc fibres 1l-diazo-6-nitro-2-hydroxynapthalene-4-sulfonic urea of1-(4-ami ophenyl)--ph ny1-5-pymz0lone red. 1dureaof1-(4-amino-plienyl)-3-ethyl-5-pyrazolone red. urea of 1-(4-amino-2'-chlorophenyl)-3-metliyl-5-pyrazo1one red, urea ofl-(4-amino-2-methyl henyl)-3-methyl-5-pyrazo1one.-. red. urea ofl-(4-amino-2-methy phenyl)-3-methyl-5-pyrazolone red. urea of1-(4-amino-3-chlorophenyl)-3-methyl-5-pyrazolone-. red. urea of1-(4"amino-2-methoxyphenyl)-3-methyl-5-pyrazolone red. urea ofl-(4'-amino-2-bromophenyl)-3;methyl-5- yrazolone red. urea ofll-iheuyl-(y-phenyl-3:2"-dimethyl-4 -amino)-3-methyl5 red.

on th fig of l-gy-amino-3-methylphenyl)-3-methyl-5-pyrazolone red.thiourea of l- 4'-amino-2-chlorophenyl)-3methyl-5-pyrazolone red.thioureaof1-(4-aminophenyl)-3-phenyl-5-pyrazolone red thiourea oi1-pl1eny1-(4 -phenyl-4"-amino)-3-methyl-5-pyrazolone. red.

duced which can be isolated in form of the colorless crystallinehydrochloride.

On interaction of other acyl-acetic esters or What I claim is: 1. Aprocess for the manufacture of a metallisable monoazo dyestuff which, inthe free state,

substituted p-nitrophenyl hydrazines with each corresponds 130 t e formua other in equivalent quantities the corresponding 1- (4-nitrophenyl)-5-pyrazolones or 1- (4'-aminophenyD-5-pyrazolones respectively will beobtained, which with respect to their properties are very similar to theabove described 1-(4-aminophenyl) -3-phenyl-5 -pyrazolone.

EXAMPLE 3 29.5 parts of l-diazo-6-nitro-2-hydroxynaphthalene--sulfonicacid are combined with an aqueous solution of 55.6 parts of urea ofl-phenyl- (4-phenyl-4"-amino) -3-methyl-5-pyrazolone in the presence ofan excess of sodium carbonate and While cooling with ice. After stirringfor several hours at 0-10" C. the diazo compound CO- H] which comprisescoupling 1 mole of l-diazo-G- nitro 2 hydroxy naphthalene-i-sulfonicacid with 1 mole of a pyrazolone-urea of the formula the 6th group ofperiodic table whose atomic ,-#1!7B,T1 0 '6 weight not less than "1'6and not greater than phenyl radicals, and :2 stands for a member :se-'33, Y stands fora radical selectedfrom the group lected from the groupconsisting :of p-lphenylene consisting of methyl, ethyl and phenylradicals, and 4:4' diplre'riylene:radicals free from :sulfonic and Zstands for a member selected from the acid groups. group consisting ofp-phenylene and 4:4di- 5 4. Process for the manufacture of ametalphenylene radicals free from sulfonic acid groups. lisahle monoa'zofiyestufi which, in the free state,

2. A process for the manufacture of .a metalcorresponds to the formula11:02 on, on:

. HOaS N=N H-CO oo- Hg lisable monoazo dyestuff which, in the freestate, which comprises coupling 1 mole of 1-diazo-6- cofresponds'totheformula mtr'o 2 -hydroxyna-phtha lene 4 sul'fonic acid N00 with 1 moleof the pyrazoloneurea-of theformu la Y-0=N N=CY -Z-NHCNHZN/ Bo s N=NH-CO 00- H, CH8 CH8 which comprises coupling 1 mole of 1-diazo-6- Cnitro-2-hydroxynaphtha1ene-4-sulfonic acid with H 6 O H a mole of apyraz'olone-urea of the formula 2 Y-C -'N o N :'oY

\N ZNH- -NH z N/ I 5. Process for the manufacture of a metallisableJHPCO OOAJH monoazo'dyestu'ff which, in the free state, correin whichformulae Y'st'ands fora ra'dica'l's'elected sponds to the' 'formula N02OH; on,

from the group consisting of methyl, ethyl and which comprises coupling1 mole of l-diazo-G- phe'nyl radicals, and Z stands for a member senitro2 -"hydroxynaphthalene 4 sulfonic acid lected from the group consistingof p-ph'enylene with '1 mole of thepyrazolone-urea of the formula E rC-N\ N=o Hz-OO o 0 H9 and 4:4-diphenylene radicals free from sulfonic-Process for the manufacture of a metalacid groups. lis'ablemonoazodyestuff which, in the free state,

corresponds-to the formula N02 0H, CH3

3. A process for the manufacture of a metal- 7 which "comprises coupling1 mole of 1-diazo-6- lisable monoazo dyestufi which, in the free state,nitro -.2 hydroxynaphthalene 4 sulfonic acid corresponds to the formulawith 1 .mole of *the pyrazolone-thio urea of the NO2 formula Y C N\ Z /NC Y CH8 CH3 l /NZ-NH NHZ-N\ I N H038 N=N- 11-00 00- H2 l NONH CS NHON/OH Hz-CO o 0-0112 which comprises coupling 1 mole of l-diazofi- 7 Ametamsable monoazo dy stufi which, innitro-2-hydroxynaphtha1ene-4-sulfonic acid with the free state,corresponds to the formula 1 mole of a pyrazolone-thio urea of theformula N02 from the group consisting f y ethyl and wherein X stands fora metalloid of the 6th wherein Y stands for a radical selected from thegroup consisting of methyl, ethyl and phenyl 9. A metallisable monoazodyestuff which, in the free state, corresponds to the formula wherein Ystands for a radical selected from the group consisting of methyl, ethyland phenyl radicals, and Z stands for a member selected from the groupconsisting of p-phenylene and 4:4- diphenylene radicals free fromsulfonic acid groups.

10. The metallisable monoazo dyestuff which, in the free state,corresponds to the formula radicals, and Z stands for a member selectedfrom the group consisting of p-phenylene and 4:4-

NO: CH3

diphenylene radicals free from sulfonic acid 11. The metallisable monazodyestuff which, in the free state, corresponds to the formula 12. Themetallisable monoazo dyestuif which,

in the free state, corresponds to the formula groups.

N02 CH1 PETER HINDERMANN.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 1,845,426 Latten Feb. 16, 19322,185,901 Schmid Jan. 2, 1940 2,195,784 Schmid Apr. 2, 1940 2,195,787Schmid Apr. 2, 1940 2,195,788 Schmid A r. 2, 1940 2,221,360 Schmid Nov.12, 1940 2,221,361 Schmid Nov. 12, 1940 2,228,374 Stusser et al Jan. 14,1941

